EP0677497A1 - Ceramic composites having a weak bond interphase material selected from monazites and xenotimes - Google Patents
Ceramic composites having a weak bond interphase material selected from monazites and xenotimes Download PDFInfo
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- EP0677497A1 EP0677497A1 EP95101948A EP95101948A EP0677497A1 EP 0677497 A1 EP0677497 A1 EP 0677497A1 EP 95101948 A EP95101948 A EP 95101948A EP 95101948 A EP95101948 A EP 95101948A EP 0677497 A1 EP0677497 A1 EP 0677497A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/902—High modulus filament or fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2938—Coating on discrete and individual rods, strands or filaments
Abstract
Description
- The United States Government has rights in this invention under contract number N00014-91-C-0157 awarded by the Department of the Navy.
- The present invention relates to ceramic composites and, in particular, to high temperature ceramic matrix composites having a phosphate selected from monazites and xenotimes as a weak bond interphase material.
- A primary requirement for toughness in ceramic composites is the existence of a weak interface (or interphase) between constituents of the composite, such as between matrix and reinforcement materials. A weakly bonded interface allows sliding between the reinforcements and the matrix and/or preferential crack deflection around the reinforcements for optimal toughening of the composite. In fibrous composites the weak interface allows the matrix to crack and/or deform without rupturing the fibers. In particulate composites clouds of microcracks can form around a large crack and disperse the rupture process. In multilayered composites the individual layers can fracture independently and disperse the rupture event to produce a non-catastrophic response.
- An ideal interface between a reinforcement and a ceramic matrix must be sufficiently weak to allow debonding and sliding of the reinforcement when a crack impinges upon it from the matrix. If this does not occur, the crack passes through the reinforcement with minimal or no toughening of the composite. A relevant property of the interface is the debond energy, Γi, of either the interphase material or the actual interfaces between the reinforcement, interphase material, and matrix. The debonding criterion is generally satisfied if Γi/Γf ≲ 0.25, where Γf is the fracture energy of the reinforcement.
- Ceramic composites are desirable in certain applications because of their refractory properties. For a high temperature composites, however, further requirements are imposed on the interphase material: it must be weak and stable over the entire temperature range of use, chemically compatible with the matrix and fiber, and morphologically and environmentally stable at high temperatures. Existing fibrous and multilayered ceramic composites rely on carbon, boron nitride, or micaceous materials (e.g., fluorophlogopite) to provide the weak interface. Examples of these composites include various glasses, glass ceramics, silicon carbide, and silicon nitride reinforced with SiC or Al₂O₃ fibers; alumina, silicon nitride, or MoSi₂ reinforced with SiC whiskers; and multilayered laminates having layers of SiC and carbon. At higher temperatures, however, carbon and boron nitride interphase materials oxidize readily and micaceous materials react with reinforcement and matrix materials.
- Machinable glass ceramics are another example of ceramic composites that rely on easy debonding. These composites contain platelets of a mica, such as fluorophlogopite, that cleave easily and cause chipping when the surface is contacted by a hard point. Because of this easy chipping, the material can be shaped using conventional metal working processes such as milling, drilling, and turning that remove material at a single contact site (rather than the more expensive and less versatile multipoint grinding that is needed for most ceramics).
- Composites containing layers of interface materials selected from the β-alumina/magnetoplumbite family of structurally related materials have been developed for use in high temperature, oxidizing environments. These materials are described in U.S. Pat. No. 5,137,852 issued to Morgan et al., the teachings of which are incorporated herein by reference. Experimental work with these materials has shown, however, that it is difficult to find suitable composite systems comprising a ceramic matrix; reinforcements having high strength and high Young's modulus; and a weakly bonded interface material that is morphologically stable in high temperature oxidizing environments, chemically compatible with the matrix and fiber system, and a good match to the thermal expansion of the matrix and fibers. Because most suitable reinforcements and matrices are multiphase materials, the compatibility of the materials is reduced, particularly over a range of temperatures, and the complexity of chemical processing is increased. Thus, there is a need for high temperature ceramic composites that are less complex, have a weakly bonded interface between reinforcement and matrix materials, and are morphologically stable in high temperature oxidizing environments.
- The present invention comprises a family of ceramic composite materials that include a monazite or xenotime and are stable in oxidizing environments at temperatures up to about 2000°C. Monazite or xenotime functions as a weak bond interphase material between the constituents of the composite. Monazite comprises a family of phosphates having the form MPO₄, where M is selected from the larger trivalent rare earth elements of the lanthanide series (generally La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, and Tb) and coupled substituted divalents and tetravalents such as Ca or Sr with Zr or Th. Xenotimes are phosphates similar to monazite, where M is selected from Sc, Y, and the smaller trivalent rare earth elements of the lanthanide series (generally Dy, Ho, Er, Tm, Yb, and Lu). High temperature ceramic composites that include a monazite or xenotime and exhibit damage tolerant behavior or non-catastrophic fracture (i.e., toughness) can be fabricated in a variety of material systems and reinforcement morphologies, including multilayered laminar composites; fiber, whisker, and particulate reinforced composites; and hybrid laminar composites. Alumina fibers (Al₂O₃), as an example of a preferred reinforcement material, have a high Young's modulus and may be used in single crystal or polycrystalline form. In preferred embodiments, the ceramic matrix comprises a material similar to the reinforcement to improve compatibility of the composite materials. The interphase material allows debonding and "frictional" sliding between the constituents of the composite and inhibits crack growth across the interface.
- A principal object of the invention is improved toughness in ceramic composites. A feature of the invention is a monazite or xenotime included as a weak bond interphase material in ceramic composites. An advantage of the invention is formation of ceramic composites that are morphologically stable in high temperature oxidizing environments.
- For a more complete understanding of the present invention and for further advantages thereof, the following Detailed Description of the Preferred Embodiments makes reference to the accompanying Drawings, in which:
- FIGURE 1 is a schematic cross section showing crack deflection and debonding in a fiber reinforced ceramic composite of the present invention;
- FIGURE 2 is a schematic cross section showing crack deflection and debonding in layers of a ceramic composite of the present invention;
- FIGURE 3 is a schematic cross section showing crack propagation through multiple layers of a laminar ceramic composite of the present invention; and
- FIGURE 4 is a schematic cross section showing a hybrid laminar ceramic composite of the present invention.
- The present invention comprises a family of high temperature ceramic composites having an interphase material that provides a weakly bonded interface between the constituents of the ceramic composite. The interphase material, which is chosen for high temperature compatibility with the matrix and any reinforcement materials to provide a weakly bonded interface, is selected from the monazites and xenotimes. Monazite comprises a family of phosphates having the form MPO₄, where M is selected from the larger trivalent rare earth elements of the lanthanide series (generally La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, and Tb) and coupled substituted divalents and tetravalents such as Ca or Sr with Zr or Th. Xenotimes are phosphates similar to monazite, where M is selected from Sc, Y, and the smaller trivalent rare earth elements of the lanthanide series (generally Dy, Ho, Er, Tm, Yb, and Lu). By way of example, the ceramic matrix material is generally selected from the group consisting of Al₂O₃, MgAl₂O₄, ZrO₂, monazites, xenotimes, mullite, and mixtures of the foregoing. The reinforcement material is generally selected from the group consisting of Al₂O₃, MgAl₂O₄, ZrO₂, mullite, and mixtures of the foregoing, and may be in the form of fibers, whiskers, or particulates. The interphase material allows "frictional" sliding between constituents of the ceramic composite and inhibits crack growth across the interface.
- LaPO₄, or La-monazite, is a preferred interphase material in ceramic composites of the present invention because of its formation of a weak bond with alumina (Al₂O₃). Unfortunately, there are no known phase diagrams in the published literature involving monazite or xenotime and selected matrix materials. This omission indicates an oversight of the community regarding the unexpected and useful ceramic properties of these phosphates. For example, LaPO₄ is a refractory material with no decomposition up to its melting point of 2072 ± 20°C. In addition, LaPO₄ is not easily reduced-it survives hot pressing in graphite to 1400°C when not in direct contact with the solid graphite. The coefficient of thermal expansion (CTE) of monazite has been measured at 9.7 × 10⁻⁶ ± 0.1 × 10⁻⁶ °C⁻¹ from room temperature to 1000°C. Monazite is non-toxic and insoluble in water and acids, which provides high temperature stability against stress corrosion in the humid atmosphere of combustion gases, for example.
- The following descriptions and examples regarding LaPO₄ as a preferred interphase material also apply, in general, to the monazite and xenotime family of phosphates when used in ceramic matrix composites of the present invention. A preferred embodiment of the present invention comprises a ceramic composite system based on alumina (Al₂O₃) and LaPO₄ that is stable in high temperature oxidizing environments. The bond between LaPO₄ and alumina is sufficiently weak to allow debonding, and the materials are compatible and morphologically stable in oxidizing and reducing atmospheres at temperatures up to about 2000°C. Other potential interphase materials for alumina composites, such as C, BN, or refractory metals Mo, Cr, W, and Pt, are not oxidation resistant and can cause degradation of the fibers. Tin dioxide (SnO₂) can be used to provide a diffusion barrier and a weak interface between alumina fibers and glass or alumina matrices, but it is not stable in reducing atmospheres and it reacts slightly with various glasses.
- Initial compatibility tests of preferred embodiments indicate that although no reactions and no eutectic occur between Al₂O₃ and LaPO₄ at temperatures up to about 1750°C, there is a small solid solubility of Al₂O₃ in LaPO₄ (barely discernible by x-ray diffraction). To ensure that this solid solution limit was exceeded, the LaPO₄ powder used to fabricate composites was prereacted with a small amount of alumina by firing at 1100°C with the addition of 1% by weight of AlOOH (Disperal® solution).
- Sapphire fibers were coated with LaPO₄ by dipping reinforcing fibers, such as sapphire fibers, for example, into a slurry of LaPO₄ powder in iso-butanol. The coated fibers were embedded in α-Al₂O₃ powder and then placed in a graphite die and hot pressed at 1400°C for 1 hour in a nitrogen atmosphere. Slices of the composite were cut and polished for testing. A schematic cross section of such a composite 10 is illustrated in Figure 1, showing
alumina matrix 12, reinforcingfiber 14, andLaPO₄ coating 15. - In the tests, both
alumina matrix 12 and theLaPO₄ coating 15 were fully dense and no reactions between the LaPO₄ andmatrix 12 or LaPO₄ andfibers 14 were observable by scanning electron microscopy.LaPO₄ coating 15 was continuous but not uniform-its thickness varied between approximately 1 µm and 20 µm but the variation had no effect on the results. A Vickers indenter, a square based diamond pyramid used for testing hardness of materials (as gauged by the size of the square indentation area 18), was used to generatecracks 16 in ceramic composite 10 oriented normal to the surface and aligned along the diagonals of thecontact area 18. Indentation cracks 16 generated by the Vickers indenter inAl₂O₃ matrix 12 always deflected at the interface ofLaPO₄ coating 15 andfiber 14 as indicated in Figure 1. Additional cracking occurred inLaPO₄ coating 15 in the region where the indentation crack impinged on the coating.Interfacial debonding 19 also occurred on the opposite side offiber 14.Debonding 19 was isolated from theindentation crack 16 and was caused by the tensile residual stress field of the indentation. - The debonding and sliding characteristics of the
interface coating 15 were tested by using a flat ended indenter to push on the end offiber 14 in a thin slice (1 mm thickness) ofcomposite 10 in whichfiber 14 was oriented normal to the slice. This caused debonding of the entire interface followed by sliding offiber 14 out of the hole. Examination of the newly exposed surfaces of pushedfiber 14 and the remaining hole by scanting electron microscopy indicated that the separation occurred exactly along the interface betweenLaPO₄ coating 15 andsapphire fiber 14. This test indicates that the Al₂O₃, LaPO₄ and sapphire composite system possesses the debonding and sliding characteristics needed for a tough composite. - Slices of composite 10 containing
fibers 14 normal to the surface were polished then heated in air to various temperatures for various times to test the stability of theinterface coating 15. After heating, the interfacial debonding was tested using the indentation cracking method described above. In all cases (the most severe being 1600°C for 24 hours) the interfaces debonded when the indentation crack intersected them. After long heat treatments at temperatures up to 1400°C, there was no evidence of any reaction or change in interfacial morphology internally (except for some grain growth in the monazite to a grain size of ~ 5 to 10 µm) or on the exposed surface. After heat treatment at 1600°C there were no changes internally (i.e., examination of surface after polishing off ~ 10 µm of the exposed surface). However, on the exposed surface there were plate-shaped β-alumina/magnetoplumbite grains formed at the interfaces between the alumina and the monazite (more so between the matrix and monazite than between the monazite and the fibers). These grains were a Mg-Ca-La-aluminate, which was apparently stabilized by Mg that originated from the matrix (the alumina powder used for the matrix contained 0.5% MgO as an additive to control grain growth). Such plateshaped grains were not observed when a high purity alumina was used. - In a variation of the composite described above,
sapphire fibers 14 were placed in a graphite die with LaPO₄ powder and hot pressed at 1300°C for 1 hour in a nitrogen atmosphere. This produced a composite similar to that of Figure 1, except that LaPO₄ formed the entire matrix instead of merely a coating aroundfibers 14. Sections of the composite were cut normal to the fiber direction using a diamond saw and polished with diamond powder to allow microstructural characterization and testing of fracture properties. - The LaPO₄ matrix was close to fully dense and no reaction with
sapphire fibers 14 was observable by scanning electron microscopy. Several tests were done to assess the interfacial debond properties, including loading a Vickers indenter into the matrix near afiber 14 as shown in Figure 1. As described above, when acrack 16 intersected asapphire fiber 14, crack 16 was deflected around the fiber-matrix interface, similar to that illustrated in Figure 1, rather than passing into and throughfiber 14. - Another test involved flexural loading of a thin slice of
composite 10, containingfibers 14 oriented normal to the slice, until the slice fractured. Where the fracture intersectedfibers 14 it deflected around the interface leaving clean separation of the fibers and matrix. These results show that the interface between LaPO₄ and sapphire has sufficiently low fracture energy for use in tough ceramic composites. - Laminar composites of the present invention were fabricated using two colloidal methods. In both cases separate slurries of alumina (Sumitomo powder without Mg additive) and LaPO₄ powders were prepared as follows: the powders were dispersed ultrasonically in water at pH 2 and NH₄NO₃ was added to 2M resulting in suspensions that coagulated and allowed particles to pack to high density. In one method the multilayered composite was formed by alternately adding measured amounts of the two suspensions to a cylindrical container and centrifuging the container between each addition. This formed uniform, alternating, densely packed layers of the two powders which, after drying, were sintered to full density by heating in air at 1600°C for 2 hours. Specimens with various layer thicknesses (as small as approximately 2 µm) were prepared in this manner. In a second method, multilayered composites were formed by alternately vacuum slip casting measured amounts of the two suspensions to form a layered compact which was then surrounded by alumina powder and hot pressed in graphite dies at 1400°C for one hour.
- Interfacial debonding was tested on specimens with thick (> 100 µm) Al₂O₃ layers 22 and thin (~ 2 to 20 µm) LaPO₄ layers 24 using
Vickers indentations 18 placed near athin layer 24 as shown in Figure 2.Cracks 26 fromindentation 18 were arrested byLaPO₄ layer 24, which debonded along the interface with the next layer of Al₂O₃. - Interfacial debonding of a multilayer laminar composite 30 was tested by loading notched beams as indicated by
arrows 32 in Figure 3.Crack 34 that initiated fromnotch 36 intop Al₂O₃ layer 22 was arrested at thefirst LaPO₄ layer 24, which then debonded along the interface with thenext Al₂O₃ layer 22. After increasing the applied load, anew crack 38 initiated independently in thenext Al₂O₃ layer 22 and the sequence of crack growth, debonding, and new initiation repeated throughout the specimen as illustrated in Figure 3. - Slices of composite 30 with polished surfaces were heat treated as in Example 1 above to test the stability of the LaPO₄ layers 24 and interfaces. The only changes detected after heat treatment at temperatures up to 1600°C and times up to 24 hours were grain growth in both the alumina (grain size up to 50 µm) and monazite (grain size up to 20 µm). There were no signs of adverse reactions or changes in interface morphology (without Mg in the matrix, the β-alumina grains did not form on the exposed surface at 1600°C as they did in Example 1 above).
- Hybrid
laminar composites 40 consisting of polycrystalline alumina layers 42 alternating with LaPO₄ layers 44 reinforced withsapphire fibers 46, as shown in Figure 4, were fabricated using the colloidal method described above in Example 3. LaPO₄ layers 44 were built in several steps using a vacuum slip casting method as follows: athin layer 44 of LaPO₄ was deposited on top of aprevious Al₂O₃ layer 42,fibers 46 were laid in place, and the remainder ofLaPO₄ layer 44 was added. These steps were simply repeated to build up multilayer hybridcomposite structure 40. The same tests as in Example 3 above were used to assess interfacial debonding, with similar results being obtained. In the notched beam tests an additional effect of debonding and pullout of the sapphire fibers within the LaPO₄ was observed. Such fiber pullout is expected to improve the toughness of laminar composites. - Particulate composites of the present invention were fabricated of LaPO₄ and Al₂O₃ using the following colloidal method: powder slurries of Al₂O₃ and LaPO₄ were prepared as described above in Example 3, then measured amounts of the two slurries were mixed together using ultrasonic agitation to achieve uniform mixing. Mixtures containing ratios 1:3, 1:1, and 3:1 of Al₂O₃:LaPO₄ by volume were prepared. Testing indicated that these particulate composites are machinable, and the Al₂O₃:LaPO₄ ratio can be optimized for specific end use applications.
- Although the present invention has been described with respect to specific embodiments thereof, various changes, modifications, and substitutions may be suggested to one skilled in the art. Therefore, it is intended that the present invention encompass such changes and modifications as fall within the scope of the appended claims.
Claims (7)
- A tough, high temperature ceramic composite (10, 30, 40), comprising:
a first ceramic material (12, 14, 22, 42); and
a second ceramic material (15, 24, 44) selected from the group of phosphates consisting of monazites and xenotimes, said second ceramic material (15, 24, 44) forming a weak bond interface with said first ceramic material (12, 14, 22, 42). - The high temperature ceramic composite (10, 30, 40) of Claim 1, wherein said first ceramic material (12, 22, 42) comprises a material selected from the group consisting of Al₂O₃, MgAl₂O₄, ZrO₂, monazites, xenotimes, mullite, glasses, glass ceramics, silicon carbide, silicon nitride, MoSi₂, and mixtures of the foregoing.
- The high temperature ceramic composite (10, 40) of Claim 1, further comprising a reinforcement material (14, 46) having a form selected from the forms consisting of fibers, whiskers, and particulates, wherein said second ceramic material (15, 44) forms said weak bond interface between said first ceramic material (12, 42) and said reinforcement material (14, 46).
- The high temperature ceramic composite (10, 40) of Claim 3: wherein said reinforcement material (14, 46) is selected from the group consisting of Al₂O₃, MgAl₂O₄, ZrO₂, SiC, mullite, and mixtures of the foregoing.
- The high temperature ceramic composite (10, 40) of Claim 3, wherein said first ceramic material (12, 42) comprises alumina, said second ceramic material (15, 44) comprises LaPO₄, and said reinforcement material (14, 46) is selected from the group consisting of sapphire fibers and polycrystalline alumina fibers.
- The high temperature ceramic composite (30) of Claim 1, wherein the composite (30) comprises a plurality of alternating layers of said first ceramic material (42) and said second ceramic material (44).
- The high temperature ceramic composite (40) of Claim 1, wherein the composite (40) comprises a hybrid laminar composite having a plurality of layers of said first ceramic material (42) alternating with a plurality of layers of said second ceramic material (44), each of said layers of said second ceramic material (44) including a reinforcement material (46).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US22805994A | 1994-04-15 | 1994-04-15 | |
US228059 | 1994-04-15 |
Publications (2)
Publication Number | Publication Date |
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EP0677497A1 true EP0677497A1 (en) | 1995-10-18 |
EP0677497B1 EP0677497B1 (en) | 1998-12-02 |
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EP95101948A Expired - Lifetime EP0677497B1 (en) | 1994-04-15 | 1995-02-13 | Ceramic composites having a weak bond interphase material selected from monazites and xenotimes |
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Country | Link |
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US (1) | US5514474A (en) |
EP (1) | EP0677497B1 (en) |
JP (1) | JP2901895B2 (en) |
CA (1) | CA2137528C (en) |
DE (1) | DE69506304T2 (en) |
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CN113651627B (en) * | 2021-07-28 | 2022-10-14 | 航天特种材料及工艺技术研究所 | Preparation method and application of alumina fiber reinforced alumina ceramic matrix composite |
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EP0411208A1 (en) * | 1989-07-04 | 1991-02-06 | TDK Corporation | Ceramic material and method for making the same |
EP0417493A2 (en) * | 1989-08-14 | 1991-03-20 | Aluminum Company Of America | Fiber reinforced composite having an aluminum phosphate bonded matrix |
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- 1994-12-07 CA CA002137528A patent/CA2137528C/en not_active Expired - Lifetime
-
1995
- 1995-02-13 EP EP95101948A patent/EP0677497B1/en not_active Expired - Lifetime
- 1995-02-13 DE DE69506304T patent/DE69506304T2/en not_active Expired - Lifetime
- 1995-04-14 JP JP7089263A patent/JP2901895B2/en not_active Expired - Lifetime
- 1995-04-19 US US08/424,767 patent/US5514474A/en not_active Expired - Lifetime
Patent Citations (4)
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EP0043643A1 (en) * | 1980-06-30 | 1982-01-13 | Corning Glass Works | Glass-ceramic as matrix for incorporation of radioactive wastes and for inorganic fiber composites, and production of such glass-ceramics |
EP0366234A1 (en) * | 1988-10-24 | 1990-05-02 | Corning Incorporated | Fiber-reinforced composite comprising mica matrix or interlayer |
EP0411208A1 (en) * | 1989-07-04 | 1991-02-06 | TDK Corporation | Ceramic material and method for making the same |
EP0417493A2 (en) * | 1989-08-14 | 1991-03-20 | Aluminum Company Of America | Fiber reinforced composite having an aluminum phosphate bonded matrix |
Also Published As
Publication number | Publication date |
---|---|
CA2137528A1 (en) | 1995-10-16 |
DE69506304T2 (en) | 1999-04-29 |
EP0677497B1 (en) | 1998-12-02 |
CA2137528C (en) | 2001-07-03 |
JPH07291713A (en) | 1995-11-07 |
US5514474A (en) | 1996-05-07 |
DE69506304D1 (en) | 1999-01-14 |
JP2901895B2 (en) | 1999-06-07 |
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